Condensation products



Wotentod Nov. i4, 39

STATES PATENT osncc GONDENSATION PRODUCTS Wilhelm miller. Wussiurz. Germany. ll sinlor to Winthrop chemieol'colnplny, Inc New York, N. 2., a corporations! New York No Drawing. Application Deoembes 31, 19*],

In German Burial No. 1823. M3?

Janna-yd,

c cum. (cl. see-4st) This invention relates to condensation products oi i-nmethpi-cyciopentene-(l) -one-(t) with compounds hovins e system of two reactive eon- .iucuted double hands and to 9. process of pre- 5 purine the sold condensation products.

Cvciic hetones which ere unsaturated in the mp-position to the keto group have a tendency to underpo onto condensation with the formation ot resinous products. This tendency is increas- 1 inc icons the cycloheptenone over the cyciohexenone to the cvclopentenone.

Cpclopentndienones ore iikewise Mom to ionn nuto condensation products, for instance, two molecules oi tetrechloro-cyclopentadienone com- 15 hine with one another according to the reaction neechonism oi the so cslied diene-synthesis in occordnnce with the toilovirim, reaction scheme:

in the new condensation products the nuclear cut-hon ntomsi end 2 ot the i-inethyi-eyclopentene-(i)-one-() urciinited to the u-carhon ntonns in the icud t-positions of the conjugated no doubts hond svstene While forming n sin-memhered cnrhon cine.

Suitnhle diene compounds ore for instance hutndiene end its suhstitution products, such as methviend diinethyi-hutndiene, furthermore,

55 cyclic compounds which either contnin the two o cyclic ketone conresetive doubiehonds in conjugated position in a carbocyclic ring or contain one double bond in e carbocyciic vrim; and the other double bond in an aliphatic side chain in conjugated position to the said ring double bond, for instance in n vinyl or propenyl side chain. Suitable compounds oi this Hod are for instance 'i-vinyl-cyeioheuene- (1)-compounds. furthermore, l-vinyi-td-dihydro-naphthaiene-compounds, end the like. When using these compmmds in the reaction two i'ormulae are possible tor the reaction products, for instance, the product obtainm i'rom 1-vinyi-3,tdihydro-naphthelene and i-methyi-cvciopentene-(D-one-(t) may have one oi the toiiowinp formuloe:

it cannot be decided ct this time which oi the two iormuiae is to he attributed to those compounds in which the dis-carbon ring formed in the reaction contains suhstituents in asymmetric positions. Generally spoken. the new condense.- tionproducts contain a cyclopentcnone ring condensed with a six-carbon ring a. carbon ctom which is common to both rings being substituted hy a. methyl group.

The condensation is pcriormcd with heating end it is ow thct even temperatures oi shout out" C. mop he used. For edecting the condensation desorihed the emotion is advantasc usly mm ut in on inert utmosphere, ice

instc cc, corhon dionde or nitmgen atmosphere in a closed pressure vmei. The l-methyi-cyeiopentene-(i) one-(5) is suitehly used in encess so thnt it nimuitnnmusiy serves as a. diluent, but else other suituhie solvents or diluent's may he employed.

The products employed in accordance with the present invention are of general commercial interest. Those compounds containing the'cyciopentenone' ring condensed with the phenam' throne ring system ere of particular interest with respect to the synthesis oi hormone-like suhstences; for instance, by the condensction oi l-methyl-cyciopentene-(l) -one-(5) with i-vinyld-methom-td-dihpdroncphthnlene end snponi- "I be iication or the methoxy group in the condensation product formed oestrous-like products are obtained.

The invention is further illustrated by the following examples without being restricted thereto:

Example 1.- -40 parts by weight of l-methylcyclopentene-(1)-0ne-(5) are heated with 20 parts by weight of 2,3-dimethyl-butadiene in a carbon dioxide atmosphere for 15 hours at 200 C. The reaction product is subjected to fractional distillation. The trimethyltetrahydro-indanone or the formula:

Ba 0 mo-o t om Etc-l 47-438:

c H: is obtained in the form oi-a colorless oil boiling at 129 to 130 C. under 12 mm. pressure.

Example 2.2.3 parts by weight of l-vinylcyclohexene-(l) are heated with 10 parts by weight 0! 1-methyl-cyclopentene-(1) -one-(5) in a nitrogen atmosphere in a pressure vessel for 16 hours at 1'70 C. When subjecting the reaction product to fractional distillation, 2.2 parts by weight of the condensation product havin one of the formulae are obtained in the form 01' a colorless oil which boils at 104 to 105 C. under 0.1 mm. pressure. The first running of the distillation may be used in another condensation reaction.

Example 3.'l parts by weight of l-vinylcyclohexene-(l) are heated in a pressure vessel with 22 parts by weight of 1-methy1-cyclopentene-(ll-one-(5) in a. nitrogen atmosphere for 24 hours at 205 C. On fractional distillation 10.2 parts by weight of the condensation product are again obtained as a colorless oil boiling at 104 to 105 C. under 0.1 mm. pressure.

Example 4.15 parts by weight of 1-vinyl- 3,4-dihydro-naphthalene are heated with 50 parts by weight of 1-methy1-cyclopentent-(1)- one-(5) in a'nitrogen atmosphere for 22 hours at 160 C. On fractional distillation of the reactionmixture under reduced pressure the condensation product which has one of the formulae indicated on page 1, column 2, boils at 160 to 180 C. under 0.05 mm. pressure.

With dinitrophenyl-hydrazone yellow crystals of the dinitrophenyl-hydrazone of the condensation product are obtained which melt at 186 to 189 C.

The 1-vinyl-3,4 dihydronaphthalene is prepared as follows:

A solution of. 25 grams of 1-keto-i,2,3,4-tetrahydronaphthalene in 150 cos. of dicxane is saturated with acetylene in a pressure vessel at room temperature, 12 g. 0! sodium-'acetylenide are added and the mixture shaken for 40 hours at about 50 C. Then the mixture is poured into a solution of 20 ccs. ct acetic acid in 400 cos. 0! water. The oil which has precipitated is extracted with methylene chloride and the methylene chloride solution ireed from the methylene chloride after drying with calcium chloride. On fractional distillation of the residue the l-acetylenyl-1-hydroxy- 1,2,3,4 tetrahydronaphthalene is contained in the fraction boiling at 136 to 150 C. under12 mm. pressure. For removing certain quantities of the starting material, the reaction product is treated with phenyl hydrazine, ether is then added to the mixture, the ethereal solution washed with water. dilute acetic acid and sodium bicarbonate solution and dried with calcium chloride. The ether is then removed and the residue fractionated. The I-acetylenyll-hydroxy 1,2,3,4 tetrahydronaphthalene boils under 0.2 mm. pressure at'102 to 104 C. (yield about 15 g.).

15 grams of the product obtained are dissolved in 150 cos. of alcohol and heated to boiling under reflux for 7 hours with 30 g. of coppered zinc dust. The cold, clear solution is poured oil from the sludge, the latter three times extracted with 50 cos. of ether, then sucked of! and washed with 50 cos. of warm ether. The combined solutions are diluted with 350 cos. of water, the ethereal layer is separated oflf, dried with sodium sulfate and the solvent distilled oflf under reduced pressure. The 1-vinyl-1hydroxy- 1,2,3,4-tetrahydronaphthalene is obtained from the residue by fractional distillation in the form of a colorless oil boiling under 0.1 mm. pressure at 93 to C. (yield about 12 g.).

A solution of 5 g. 01 the 1-vinyl-1-hydroxy- 1,2,3,4-tetraiiydronaphthalene, 0.1 g. of hydroquinone and 0.1 g. of pyrogallol in 50 cos. oi! ether are gradually added to a suspension of 10 g." of phosphorus pentoxide in cos. of ether. The mixture is shaken for a short time, whereupon the phosphorus pentoxide forms lumps. Then again 5 g. of phosphorus pentoxide are added. After 45 minutes further shaking, the clear solution is filtered, the phosphorus pentoxide washed with ether and the ether removed under reduced pressure. 2.6 g. of I-vinyl-SA-dihydronaphthalene are obtained from the residue by fractional distillation in the form of a light oil boiling under 0.1mm. pressure at 62 to 63 C.

I claim:

1. The process which comprises reactin upon a compound having a system of two reactive conjugated double bonds with l-methyl-cyclopentene-(1)-one-(5) while heating.

2. The process which comprises reacting upon a carbocyclic compound a six-carbon-ring of which contains a reactive double bond in conjugated position to the double bond of a vinyl substituent with 1-methy1-cyclopentene -(1) one (5) while heating.

3. The process which comprises'reacting upon a 1-vinyl-3,4-dihydronaphthalene with l-methylcyclopentene-(1)-one-(5) while heating.

4. The condensation products of l-methyl-cyclopentene-(l) -one-(5) with compounds containing a system of two reactive conjugated double bonds in which condensation products the nuclear carbon atoms 1 and 2 of the said l-methyl-cyclopentene-(D-one-(5) are linked to the two carbon atoms in the 1- and 4-position of the conjugated system while forming a six-membered carbon ring.

5. The condensation products of i-methyl-cyclopentene-(l) -one-(5) with compounds containing a. system of two reactive conjugated double bonds, one of which is contained in a vinyl group substituting a carbocyclic ring system which latter contains in a six-carbon-rinz the other double bond in conjugated position to the double bond of the vinyl group, in which condensation products the nuclear carbon atoms 1 and 2 01' the said l-methyl-cyclopentene-(l) -one-(5) are linked to the two carbon atoms in the 1- and 4-position of the conjugated system while forming a sixmembered carbon ring.

6. The condensation products oi. i-methyl-cyc1opentene-(1)-one-(5) with a 1-viny1-3,4-dihysystem.

wrmmus 

